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1. Anaerobic oxidation of methane does not attenuate methane emissions from thermokarst lakes

   https://doi.org/10.1002/lno.12349  

   Lotem, Noam; Pellerin, André; Anthony, Katey Walter; Gafni, Almog; Boyko, Valeria; Sivan, Orit (April 2023, Limnology and Oceanography)

   Abstract The ongoing global temperature rise enhances permafrost thaw in the Arctic, allowing Pleistocene‐aged frozen soil organic matter to become available for microbial degradation and production of greenhouse gases, particularly methane. Here, we examined the extent and mechanism of anaerobic oxidation of methane (AOM) in the sediments of four interior Alaska thermokarst lakes, which formed and continue to expand as a result of ice‐rich permafrost thaw. In cores of surface (~ 1 m) lake sediments we quantified methane production (methanogenesis) and AOM rates using anaerobic incubation experiments in low (4°C) and high (16°C) temperatures. Methanogenesis rates were measured by the accumulation of methane over ~ 90 d, whereas AOM rates were measured by adding labeled‐¹³CH₄and measuring the produced dissolved inorganic¹³C. Our results demonstrate that while methanogenesis was vigorous in these anoxic sediments, AOM was lower by two orders of magnitude. In almost all sediment depths and temperatures, AOM rates remained less than 2% of the methanogenesis rates. Experimental evidence indicates that the AOM is strongly related to methanogens, as the addition of a methanogens' inhibitor prevented AOM. Variety of electron acceptor additions did not stimulate AOM, and methanotrophs were scarcely detected. These observations suggest that the AOM signals in the incubation experiments might be a result of enzymatic reversibility (“back‐flux”) during CH₄production, rather than thermodynamically favorable AOM. Regardless of the mechanism, the quantitative results show that near surface (< 1‐m) thermokarst sediments in interior Alaska have little to no buffer mechanisms capable of attenuating methane production in a warming climate. 

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2. DFT Analysis of Methane C−H Activation and Over‐Oxidation by [Cu ₂ O] ²⁺ and [Cu ₂ O ₂ ] ²⁺ Sites in Zeolite Mordenite: Intra‐ versus Inter‐site Over‐Oxidation

   https://doi.org/10.1002/cphc.202100580  

   Panthi, Dipak; Adeyiga, Olajumoke; Odoh, Samuel_O (October 2021, ChemPhysChem)

   Abstract Methane over‐oxidation by copper‐exchanged zeolites prevents realization of high‐yield catalytic conversion. However, there has been little description of the mechanism for methane over‐oxidation at the copper active sites of these zeolites. Using density functional theory (DFT) computations, we reported that tricopper [Cu₃O₃]²⁺active sites can over‐oxidize methane. However, the role of [Cu₃O₃]²⁺sites in methane‐to‐methanol conversion remains under debate. Here, we examine methane over‐oxidation by dicopper [Cu₂O]²⁺and [Cu₂O₂]²⁺sites using DFT in zeolite mordenite (MOR). For [Cu₂O₂]²⁺, we considered the μ‐(η²:η²) peroxo‐, and bis(μ‐oxo) motifs. These sites were considered in the eight‐membered (8MR) ring of MOR. μ‐(η²:η²) peroxo sites are unstable relative to the bis(μ‐oxo) motif with a small interconversion barrier. Unlike [Cu₂O]²⁺which is active for methane C−H activation, [Cu₂O₂]²⁺has a very large methane C−H activation barrier in the 8MR. Stabilization of methanol and methyl at unreacted dicopper sites however leads to over‐oxidation via sequential hydrogen atom abstraction steps. For methanol, these are initiated by abstraction of the CH₃group, followed by OH and can proceed near 200 °C. Thus, for [Cu₂O]²⁺and [Cu₂O₂]²⁺species, over‐oxidation is an inter‐site process. We discuss the implications of these findings for methanol selectivity, especially in comparison to the intra‐site process for [Cu₃O₃]²⁺sites and the role of Brønsted acid sites. 

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3. Methane Over‐Oxidation by Extra‐Framework Copper‐Oxo Active Sites of Copper‐Exchanged Zeolites: Crucial Role of Traps for the Separated Methyl Group

   https://doi.org/10.1002/cphc.202100103  

   Adeyiga, Olajumoke; Odoh, Samuel_O (April 2021, ChemPhysChem)

   Abstract Copper‐exchanged zeolites are useful for stepwise conversion of methane to methanol at moderate temperatures. This process also generates some over‐oxidation products like CO and CO₂. However, mechanistic pathways for methane over‐oxidation by copper‐oxo active sites in these zeolites have not been previously described. Adequate understanding of methane over‐oxidation is useful for developing systems with higher methanol yields and selectivities. Here, we use density functional theory (DFT) to examine methane over‐oxidation by [Cu₃O₃]²⁺active sites in zeolite mordenite MOR. The methyl group formed after activation of a methane C−H bond can be stabilized at a μ‐oxo atom of the active site. This μ‐(O−CH₃) intermediate can undergo sequential hydrogen atom abstractions till eventual formation of a copper‐monocarbonyl species. Adsorbed formaldehyde, water and formates are also formed during this process. The overall mechanistic path is exothermic, and all intermediate steps are facile at 200 °C. Release of CO from the copper‐monocarbonyl costs only 3.4 kcal/mol. Thus, for high methanol selectivities, the methyl group from the first hydrogen atom abstraction stepmust bestabilizedawayfrom copper‐oxo active sites. Indeed, it must be quickly trapped at an unreactive site (short diffusion lengths) while avoiding copper‐oxo species (large paths between active sites). This stabilization of the methyl group away from the active sites is central to the high methanol selectivities obtained with stepwise methane‐to‐methanol conversion. 

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4. Global Nitrous Oxide Production Determined by Oxygen Sensitivity of Nitrification and Denitrification

   https://doi.org/10.1029/2018GB005887  

   Ji, Qixing; Buitenhuis, Erik; Suntharalingam, Parvadha; Sarmiento, Jorge L.; Ward, Bess B. (December 2018, Global Biogeochemical Cycles)

   Abstract The ocean is estimated to contribute up to ~20% of global fluxes of atmospheric nitrous oxide (N₂O), an important greenhouse gas and ozone depletion agent. Marine oxygen minimum zones contribute disproportionately to this flux. To further understand the partition of nitrification and denitrification and their environmental controls on marine N₂O fluxes, we report new relationships between oxygen concentration and rates of N₂O production from nitrification and denitrification directly measured with¹⁵N tracers in the Eastern Tropical Pacific. Highest N₂O production rates occurred near the oxic‐anoxic interface, where there is strong potential for N₂O efflux to the atmosphere. The dominant N₂O source in oxygen minimum zones was nitrate reduction, the rates of which were 1 to 2 orders of magnitude higher than those of ammonium oxidation. The presence of oxygen significantly inhibited the production of N₂O from both nitrification and denitrification. These experimental data provide new constraints to a multicomponent global ocean biogeochemical model, which yielded annual oceanic N₂O efflux of 1.7–4.4 Tg‐N (median 2.8 Tg‐N, 1 Tg = 10¹² g), with denitrification contributing 20% to the oceanic flux. Thus, denitrification should be viewed as a net N₂O production pathway in the marine environment. 

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5. Methanobactin from Methanotrophs: Genetics, Structure, Function and Potential Applications

   https://doi.org/10.1093/femsle/fnaa045  

   Semrau, Jeremy D (January 2020, FEMS microbiology letters)

   Aerobic methane-oxidizing bacteria of the Alphaproteobacteria have been found to express a novel ribosomally synthesized post-translationally modified polypeptide (RiPP) termed methanobactin (MB). The primary function of MB in these microbes appears to be for copper uptake, but MB has been shown to have multiple capabilities, including oxidase, superoxide dismutase and hydrogen peroxide reductase activities, the ability to detoxify mercury species, as well as acting as an antimicrobial agent. Herein, we describe the diversity of known MBs as well as the genetics underlying MB biosynthesis. We further propose based on bioinformatics analyses that some methanotrophs may produce novel forms of MB that have yet to be characterized. We also discuss recent findings documenting that MBs play an important role in controlling copper availability to the broader microbial community, and as a result can strongly affect the activity of microbes that require copper for important enzymatic transformations, e.g. conversion of nitrous oxide to dinitrogen. Finally, we describe procedures for the detection/purification of MB, as well as potential medical and industrial applications of this intriguing RiPP. 

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